Processes for breaking petroleum emulsions



United States Patent 3,202,615 PROCESSES FOR BREAKING PETROLEUMEMULSIONS Willard H. Kirkpatrick, Sugar Land, and Virgil L. Scale,Houston, Tex., assignors to Valco Chemical Company, Chicago, 11]., acorporation of Delaware No Drawing. Original application June 8, 1959,Ser. No. 818,563. Divided and this application June 25, 1952, Ser. No.205,068

8 Claims. '(Cl. 252-342) This application is a divisional application ofour copending application Serial No. 818,563, filed June 8, 1959, thelatter application being a continuation-in-part of our applicationSerial No. 632,647, filed January 7, 1957, both abandoned.

This invention, in general, relates to the treatment of emulsions ofmineral oil and water, such as petroleum emulsions commonly encounteredin the production, handling and refining of crude mineral oil for thepurpose of separating the oil from the water.

Petroleum emulsions are, in general, of the water-inoil type wherein theoil acts as a continuous phase for the dispersal offinely-dividedparticles of naturally oc curring waters or brines. These emulsions areoften extremely stable and will not resolve on long standing. It is tobe understood that water-in-oil emulsions may occur artificially,resulting from any one or more of numerous operations encountered invarious industries. The emulsions obtained from producing wells and fromthe bottom of crude oil storage tanks are commonly referred to as cutoil, emulsified oil, bottom settlings and BS.

One type of process involves subjecting an emulsion of the water-in-oiltype to the action of a demulsiiying agent of the kind hereinafterdescribed, thereby causing the emulsion to resolve and stratify into itscomponent parts of oil and water or brine after the emulsion has beenallowed to stand in a relatively quiescent state.

One object of our invention is to provide a novel and economical processfor resolving emulsions of the character referred to into theircomponent parts of oil and water or brine. I

Another object is to resolve water-in-petroleum oil emulsions with newcompounds which are surface-active at oil-water interfaces in a mannerto cause or aid in the breaking of the emulsion.

The treating agents employed in accordance with the present inventionconsist of compositions of high molecular weight which are organicpolycarboxy acid mixed esters of (a) oxyalkylatedorganic-solvent-soluble phenolformaldehyde condensation products whereinthe phenol reactant is a difunctional, monoalkyl phenol, the alkyl grouphaving between 4 and 15 carbons inclusive, preferably 515 carbons, andis in the ortho or para position and (b) polyoxyalkylene glycols havinga molecular weight of at least 1200 and usually not greater than 7500.Dialkyl, monofunctional phenols are not suitablefor purposes of thisinvention, but amounts up to 25% dialkyl phenol in monoalkyl phenol maybe tolerated. The weight ratio of alkylene oxide to thephenol-formaldehyde condensation product will, for most applications,fall between about l:2 and :1, preferably 1:2 to 9:1, respectively.

The oxyalkylene radicals of the phenol-formaldehyde condensationproducts consist of both oxyethylene and oxypropylene groups. They maybe reacted as a mixture of ethylene oxide and 1,2-propylene oxide togive heterogeneously mixed oxyethylene and oxypropylene groups in theoxyalkylene chains. Alternatively, one of the two oxides may be reactedfirst with the condensation product,

, then the other. In this manner the oxyalkylene radicals are composedof polyoxypropylene groups or polyoxyeth- 'ice ylene groups attached tothe phenolic nuclei of the condensation product and the otheroxyalkylenegroups attached thereto in terminal positions on the polyoxyalkylenechains.

There is an advantage to having the terminal group of the oxyalkylenechains as an oxyethylene group because the latter has a primary hydroxylgroup. A terminal oxypropylene group,- on the other hand, has asecondary hydroxyl group, which is more difiicult to sulfate or esterifywith the carboxy acids than the primary hydroxyl group Simultaneousreaction of a mixture of both ethylene and propylene oxide probablygives an oxyalkylated product having both types of terminal hydroxylgroups.

The polyoxyalkylene glycols may be either polyoxypropylene glycol or amixed oxide glycol of propylene oxide and ethylene oxide where theweight ratio of oxyethylene to oxypropylene does not exceed 4: 1. Theweight ratio of the oxyethylated phenol-formaldehyde condensationproduct to polyoxyalkylene glycol in the resulting mixed esters of thepolycarboxy acid should be 115 to 5:1, and preferably about 1:4 to 4:1.

PHENGL-FGRMALDEHYDE CONDENSATION The phenol-formaldehyde condensationproducts are prepared by reacting formaldehyde or a substance whichbreaks down to formaldehyde under the reaction conditions, e.g.,para-formaldehyde and trioxane, and a difunctional monoalkyl phenol, byheating the reactants in the presence of a small amount of an acidcatalyst such as sulfamic acid under substantially anhydrousconditionsexcepting the water produced during the reaction. The aqueousdistillate which begins to form is collected and removed from thereaction mixture. After several hours of heating at temperaturesslightly above the boiling point of water, the mass becomes viscous andis permitted to cool to about to C. At this point a suitable hydrocarbonfraction is added, and heating is resumed. Further aqueous distillatebegins to form and heating is continued for an additional number ofhours until at least about one mol of aqueous distillate per mol ofreactants has been secured. The product is permitted to cool to yieldthe phenol-formaldehyde condensation product in a hydrocarbon solvent.The molecular weight of these intermediate condensation products cannotbe ascertained with certainty, but we would approximate that the resinsemployed herein should contain about 4 to 15, preferably 4 to 10,phenolic nuclei per resin molecule. The solubility of the condensationproduct in hydrocarbon solvents such as S0 extract would indicate thatthe resins are linear type polymers, thus distinguishing them from themore common phenol-formaldehyde resins of the cross-linked type.

The phenol component of our phenol-formaldehyde resins is entirely orprincipally a difunctional phenolone having only two of the threenormally reactive orthoand parapositions available for reaction with theformaldehyde. These phenols are mono-alkyl phenols with the alkyl groupin the paraor orthoposition having up to-about 15 carbons. Phenolssuitable for our invention are difunctional, mono-alkyl phenols havingstraight chain or branch chain alkyl groups of 4-15 carbons, preferably5-15 carbons. Examples of the phenolic component include such preferredphenols as p-n-butyl phenol, p-tertiary butyl phenol, p-amyl phenol,p-tertiary hexyl phenol, p-tertiary octyl (1,l,3,3-tetramethyl butyl-l)phenol, p-nonyl phenol, p-dodecyl phenol, a crude alkyl phenolcontaining atleast about 90% p-nonyl phenol and up to 10% dinonylphenol, and others including mixtures of ortho-and/ or para-monoalkylphenols and crude alkylate phenols containing at least 75% difunctionalalkyl & phenol-s with the remainder being primarily monofunctionalphenols.

This aspect of the invention is illustrated in the following examplesbut is not limited thereto. The parts are by weight.

Example A In a three-necked reaction flask provided with means ofmechanical stirring and a return condenser system permitting the removalof any aqueous phase formed in the course of reaction, there is added1500 parts of a crude alkylate phenol which comprises about 90% of anundistilled p-nonyl phenol containing approximately 10% ofdinonylphenol, 225 parts paraformaldehyde and 3 parts sulfamic acidwhich is present as a catalyst in the reaction. The reaction mass isheated, and at 108 C. an aqueous distillate begins to form. After threehours heating at approximately 110 C. the mass becomes quite viscous andis permitted to cool to about 100 C. At this point 600 parts of Sextract is added, and heating is resumed. Again at 110 C. furtheraqueous distillate begins to form, and heating is continued for anadditional three hours, or until approximately 141 cc. of aqueousdistillate has been secured at a maximum temperature of 212 C. Theproduct is permitted to cool to yield the finished phenol-formaldehyderesin in the hydrocarbon solvent.

Example B In a manner similar to Example A, 1000 parts of the crudealkylate phenol, 120 parts of paraformaldehyde and 2 parts sulfamic acidwere heated 2 hours at 105- 110 C. to permit reaction of the phenol andformaldehyde under conditions minimizing formaldehyde loss. Attemperatures above 110 C. vigorous reaction sets in which must becontrolled by cooling. After about 27 parts of aqueous distillate havebeen secured, the reaction comes under control and becomes exceedinglyvis cous. At this point the resin is cooled to 105 C., and 400 parts ofS0 extract is added. Heating is continued for an additional three hours,or until a total of about 75 parts of aqueous distillate have beenremoved at maximum temperature of 212 C. to yield the finishedphenolformaldehyde resin in the hydrocarbon solvent.

Example C Example D In a reaction vessel provided with a stirrer and areturn condenser system providing for the removal of water distilledover in the course of the reaction, p-amyl phenol is heated to themelting point (about 90 C.). To 5000 parts of the melted p-amyl phenolis added parts of hydrochloric acid and 20 parts of oxalic acid. Then1100 parts of paraformaldehyde is added in small proportions whilemaintaining the temperature at 90-100 C. Upon completion ofparaformaldehyde addition, the reaction mixture is held at 95 C. for twohours whereupon 750 parts of S0 extract is added to reduce theviscosity. The

temperature is raised slowly to remove approximately 610 parts ofaqueous distillate at a final maximum temperature of 230 C.

The reaction mass is thereafter held at 210 C. for one hour and thencooled to 200 C. It is then blended with 3600 parts of S0 extract.

4 Example E The procedure of Example D is repeated with the substitutionof p-tertiary butyl phenol for the p-amyl phenol.

In the preceding examples, sulfamic acid has been used as the acidcatalyst to assist in the condensation reaction. Other suitableequivalent acids which may be used in place of sulfamic acid are mineralacids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc.

As stated heretofore, intermediate phenol-formaldehyde resin shouldcontain a minimum of about 4 phenolic nuclei and should not exceed about15 phenolic nuclei. It is extremely difficult, if not impossible, toaccurately determine the molecular weight of the intermediate resinproducts. However, it is believed that the resin of Example A containsabout 10 phenolic nuclei per resin molecule, Example B, about 7 phenolicnuclei, and Example C, about 4 phenolic nuclei per resin molecule.

OXYALKYLATION OF THE CONDENSATION PRODUCTS Having prepared theintermediate phenol-formaldehyde products, the next step is theoxyalkylation of the condensation products at the OH group of thephenolic nuclei. This is achieved by mixing the intermediatephenol-formaldehyde condensation product in a hydrocarbon solvent with asmall amount of a suitable catalyst in an autoclave. The condensationproduct is heated above 100 C., and both ethylene oxide and propyleneoxide, either as a mixture or by sequential addition of first thepropylene oxide and then the ethylene oxide, or vice Versa, are chargedinto the autoclave until the pressure is in the vicinity of -100 psi.

The reaction mixture is gradually heated until an exothermic reactionbegins. The external heating is then removed, and alkylene oxide isadded at such a rate that the temperature is maintained between aboutISO-160 C. in a pressure range of to p.s.i. After all of the alkyleneoxide has been added, the temperature is maintained for an additional 10to 20 minutes to assure Some preferred embodiments of the oxyalkylated,alkyl phenol-formaldehyde condensation products and methods of theirpreparation are illustrated in the following examples wherein all partsare by weight unless otherwise stated, but the invention is not limitedthereto.

Example F In an autoclave having a two-liter capacity equipped withmeans of external electrical heating, internal cooling coils andmechanical agitation, there is charged 18 parts of the resin solution ofExample B and 1.5 parts of sodium hydroxide. Into a transfer bomb thereis introduced '23 parts of mixed oxides prepared by mixing equal partsof ethylene and propylene oxide by weight. The intermediate is heated toC. and the oxide mixture is charged into the reactor until reactorpressure is 80 psi. The reaction mixture is gradually heated until anexothermic reaction begins to take place. The external heating isremoved and the mixed oxides are then added at such a rate that thetemperature is maintained between l60 C. with a pressure range of 80 to100 p.s.i. At various stages in the reaction small samples Example G Ina manner similar to Example F a mixed oxide adduct of the resin ofExample A was prepared in which the ratio of ethylene oxide to propyleneoxide was 1 part to 2 parts. The finished product is an oxyalkylatedresin in which the ratio of mixed oxides to resin is 4 to 1.

Example H In the same facilities as used in Example F, there is charged172 parts of the resin solution of Example A and 1 part of sodiumhydroxide. Into a transfer bomb there is introduced 250 parts by weightof ethylene oxide and 250 parts of propylene oxide. The intermediate isheated to 135 C. and the mixed oxides are charged into the reactor untilthe reactor pressure is 80 p.s.i. The reaction conditions from here onwere identical with those employed in Example F. The resulting productis the mixed oxide adduct of a phenol-formaldehyde resin in which theratio of oxide to resin by weight is approximately 4 to 1.

Example J In a manner similar to Example H, using a 1 to 1 by weightratio of ethylene oxide and propylene oxide, a mixed oxide adduct of theresin of Example C was prepared in which the ratio of oxide to resin was6 to 1.

Example K In a manner similar to Example H, using a 1 to 3 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example C was prepared in which the ratio of oxide to resin was6 to 1.

Example L In a manner similar to Example H, using a 1 to 3 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example B was prepared in which the ratio of oxide to resin was2 to 1.

Example M In a manner similar to Example H, using a 3 to 1 by weight ofethylene oxide to propylene oxide, a mixed oxide adduct of the resin ofExample A was prepmed in which the ratio of oxide to resin was 1 to 1.

Example N In a manner similar to Example N, a propylene oxide adduct ofthe resin of Example C was prepared in which the ratio of propyleneoxide to resin was 6 to 1 by weight. Ethylene oxide was then added tothis oxypropylated phenol-formaldehyde resin until the finished productcontained 20% by Weight of ethylene oxide.

Example P In a manner similar to Example N, a propylene oxide adduct ofthe resin of Example A was prepared in which the ratio of propyleneoxide to resin was 9 to 1 by weight.

This oxypropylated phenol-formaldehyde resin was then further reactedwith ethylene oxide until the finished material contained 5% by weightof ethylene oxide.

Example 0 In a manner similar to Example N, a propylene oxide adduct ofthe resin of Example C was prepared in which the ratio of propyleneoxide to resin was 2 to 1 by weight. This oxypropylatedphenol-formaldehyde resin was then further reacted with ethylene oxideuntil the finished material contained 30% by weight of ethylene oxide.

Example R Into the gas charge vessel of an oxyalkylation unit is charged250 parts of ethylene oxide and 250 parts of propylene oxide. The gasesare circulated via a circulating pump to mix them thoroughly. Then 2000parts of the phenol-formaldehyde resin solution of Example D and 3.8parts of sodium hydroxide are charged into the oxyalkylation. Thereactor is purged with natural gas. The mixed oxides are added atISO-160 C. The oxyalkylation is completed at this temperature and apressure of -100 p.s.i. The gases are recycled in the unit for two hoursafter the addition of oxides is complete. The resulting product isoxyalklation product of the phenolformaldehyde resin wherein theoxyethylene and oxypropylene groups are mixed heterogeneously in theoxyalkylene adduct radicals.

Example S In a manner similar to Example R, 7200 parts of the resinsolution of Example D and 1800 parts of an ethylene oxide-propyleneoxide mixture (2 parts by Weight propylene oxide per part ethyleneoxide) are reacted in the presence of 13 parts of sodium hydroxide.

Example T ESTERIFICATION OF OXYALKYLATED CONDEN- SATION PRODUCTS ANDPOLYALKYLENE GLYCOLS WITH POLYBASIC ACIDS The next and final step in thepreparation of the compositions of our invention is the esterificationof an organic, polycarboxy acid, or in some instances the anhydridethereof, with the oxyalkylated phenol-formaldehyde condensation productspreviously described and polyoxyalkylene glycols having a molecularweight of at least 1200 and not more than about 7500. The ratio of theoxyalkylated condensation product to the polyoxyalkylene glycolpreferably ranges from 1:5 to 5:1. The polyoxyalkylene' glycol may beeither polyoxypropylene glycol or an oxyethylene, oxypropylene glycolwherein the weight ratio of oxyethylene to oxypropylene does not exceed4: 1. In most cases the esterification reaction should be carried out bysequentially adding first the polyoxyalkylene glycol and then theoxyalkylated phenol-formaldehyde condensation product. The polycarboxyacid and polyalkylene glycol are heated until an aqueous distillatebegins to form. Heating is continued until sufficient aqueous distillatehas been secured to indicate that the esterification is complete. Themass is then cooled to about C. at which point the oxyalkylatedphenolformaldehyde condensation product is added. Heating is thenresumed and continued until sufiicient aqueous distillate has beensecured to indicate completion of the esterification. After cooling, asuitable hydrocarbon fraction is added to yield the polycarboxy acidmixed ester of the polyoxyalkylene glycol and the oxyalkylatedphenol-formaldehyde condensation product in a hydrocarbon carrier.

The dicarboxy acids are aliphatic, cycloaliphatic or aromaticpolycarboxy acids. In some instances, we prefer dicarboxy acids having2-l0 carbons, and in other instances acids, e.g., dimer acids having atleast 36 carbons, such as dimerized abietic acid, dimerized linoleicacid, dimerized linolenic acid, etc., are employed. Polycarboxy acids oranhydrides thereof which may be used in the esters of our inventioninclude oxalic, maleic, malonic, succinnic, diglycolic, adipic, azelaic,sebacic, fumaric, tartronic, malic, camphoric, tartaric, phthalic, andterephthalic acids or anhydrides, VR-l polymeric acid, dimerized abieticacid, dimerized linoleic and/or dimerized linolenic acid, among others.

Emery dimer acid is essentially dilinoleic acid and is a polymer made bypolymerizing an unsaturated fatty acid containing at least twononconjugated double bonds. Such acids may also be described as polymerdrying oil acids. The term drying oil acid is used herein to mean anunsaturated fatty acid containing at least two double bonds and at leastsix carbon atoms. The polymer acids employed for the purpose of theinvention preferably consist predominantly of dimer acids but maycontain trimers and higher polymers. The preferred polymer acids arethose containing 12 to 40 carbon atoms and especially the polymers ofthe drying oil acids of the linoleic acid series, including, forexample, the polymers of sorbic acid, geranic acid, palrnitolic acid,linoleic acid and humoceric acid. It will be understood that thesepolymers may include cogeneric mixtures of polycarboxy acids.

A number of these polymer acids are available as byproduct materials.Thus, one source of the polymeric acids suitable for the purposes ofthis invention is the still residue of the dry distillation of castoroil in the presence of sodium hydroxide. VR-l acid is an acid of thistype.

VR-l acid is a mixture of polybasic acids, with an average molecularweight of about 1,000. It has an average of slightly more than twocarboxylic acid groups per molecule. It is a by-product acid, and is adark amber, rather viscous liquid. A typical sample of VR-l acid gavethe following analysis.

Acid number 150 Iodine number 36 Saponification number 172Unsaponifiable matter percent 3.7, 3.5 Moisture content do 0.86

It should be noted that it is preferred to carry out the esterificati-onreaction step-wise. In this manner, products of the desired molecularweights and physical properties are formed consistently without theformation of undesirable insoluble polymers or materials which have toohigh a molecular weight or viscosity by virtue of excessivecross-linking. The fluid properties of the esters of this inventionappear to be a definite factor in their properties as emulsion-breakingagents. In some instances simultaneous reaction of the oxyalkylatedcondensation product and the polyoxyalkylene glycol is permissible, butexperimentation is essential in order to avoid formation of infusible,insoluble resinous esters. The ratio of dicarboxy acid may be such as toprovide a finished product essentially free of unreacted carboxyl groupsor a finished product which contains a high percentage of unreactedcarboxyl groups. The esters are composed 1 to 2 mols of the dicarboxyacid for each mol of total mols of the oxyalkylated phenol-formaldehyderesin and the polyoxypropylene glycol.

The dicarboxy acid esters of thisinvention are essentially Waterinsoluble. This property is important in the emulsion breakingproperties of our compositions. For purposes herein, the esters of thecharacter herein described are considered to be Water insoluble when, atequilibrium with distilled water at 70 F., not more than 2 pants byweight dissolve per .parts of Water. Water insolubility of our esters isincreased as the proportions of the oxypropylene groups with respect tothe oxyethylene groups in the oxyalkylated phenol-formaldehyde resinsand in the polyoxyalkylene glycols becomes greater. Also, highermolecular weight fatty acids, such as dimerized acids having at least 36carbons, lessen water solubility as compared to other dicarboxy acids,heretofore mentioned, having 2-10 carbons. In all cases, our esters havesufiicient hydrophobic constituents to make the final product insolublein Water within the previous definition.

' The invention will be further understood from the following exampleswherein the parts are by weight unless otherwise indicated.

Example I In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 300 parts by Weight of apolyglycol prepared by adding 6 mols of ethylene oxide terminally to apolypropylene glycol of 2700 molecular weight. Forty parts of diglycolicacid and 50 parts by weight of a suitable hydrocarbon extract is alsoadded. These materials were heated to remove 5.2 parts of aqueousdistillate over a period of about 1 hour. The reaction mass was thencooled to 150 C. Two hundred parts by weight of oxyalkylated resin ofExample F Was added, and heat was again applied to remove aqueousdistillate in .the amount of 2.3 parts. In both processing steps thematerial was heated to a temperature in the range of 265-270 C. as amaximum final temperature. After the second heating period the materialwas cooled, and 360 parts by weight of a suitable hydrocarbon extractWas added to yield the finished product.

Example II "In a manner similar to Example I, 200 parts of oxyalkylatedresin of Example I was substituted for oxyalkylated resin of Example F.

Example III In a manner similar to Example I, 200 parts of theoxyalkyla-ted resin of Example G was substituted for the 200 parts ofoxyalkylated resin of Example F.

Example IV In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 400 parts ofpolypropylene glycol 2000, 55 parts diglycolic acid and 50 parts of asuitable hydrocarbon extract. These materials were heated to removeapproximately 7.5 parts of aqueous distillate at a maximum finaltemperature of 270 C. The reaction mass was then cooled to 150- C., and100 parts of the oxyalkylated resin of Example H was added. Thesematerials were then further processed to remove 2 parts of aqueousdistillate with a maximum final temperature of 265 C. The material wascooled, and 350 parts of a suitable hydrocarbon extract is added toyield the finished product.

Example V In a three-necked flask provided with means of mechanicalstirring and heating, there is added 400 parts of a polyglycol preparedby adding 4 moles of ethylene oxide terminally .to a mole ofpolypropylene glycol 2000. To this material 45 grams of m-aleicanhydride and 2 grams of diglycolic acid are added. These materials areheated together for a period of 6 hours at -l50 C. At the end of thisperiod of heating, 100 parts by weight of the oxyalkylated resin ofExample I was added, and

the temperature was raised to remove approximately 2 parts of aqueousdistillate with a maximum final temperature of 265 C. The material wasthen cooled, and 360 parts of a suitable hydrocarbon extract was addedto give the finished product.

The use of a small amount of diglycolic acid to neutralize the catalystas the insoluble sodium diglycollate has been found exceedinglyimportant in reactions where maleic acid or maleic anhydride is used asthe dibasic acid. Apparently the presence of small amounts of alkalinecatalyst resulting from the production of high molecular weightpolyglyeols gives rise to said reactions apparently involving theformation of derivatives of maleic acid. Alkaline catalysts are known tofavor the addition of alcohols across the maleic anhydride double bond,particularly in cases where the alcohol group is of primaryconfiguration. This reaction is objectionable for the reason that maleicacid derivatives function as cross-linking agents and under certainprocessing conditions, particularly those involving long periods ofheating at high temperatures, tend to favor the formation of rubbery,oil insoluble polymers.

Example VI In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 400 parts of apolyglycol produced by adding 8 moles of ethylene oxide terminally to apolypropylene glycol of 2000 molecular weight. Sixty grams phthalicanhydride are added, and the materials heated together for a period of 8hours at a temperature of l45-155 C. At the end of this time 100 partsof the oxyalkylated resin of Example K was added, and the material wasfurther heated to remove 3.5 parts of aqueous distillate with a maximumfinal temperature of 270 C. The material was cooled, and 360 parts of asuitable hydrocarbon extract were added to give the finished product.

Example VII In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 300 parts of a hetericmixed oxide polyglycol of 3000 molecuar weight wherein the ratio ofethylene oxide to propylene oxide is l to 3. Forty grams of diglycolicacid and 50 parts of a suitable hydrocarbon extract are added, and theabove materials heated to remove aqueous dis tillate in the amount ofparts at a maximum final temperateure of 265 C. At this point thematerial was cooled to 150 C. and 200 parts of the oxyalkylated resin ofExample E was added. The reaction mass was further heated to remove 2.5parts of aqueous distillate at maximum final temperature of 270 C. Thematerial was then cooled, and 260 parts of a suitable hydrocarbonextract was added to give the final product.

Example VIII temperature of 260 C. At this point the material is cooled,and 250 parts of the oxyalkylated resin of Example L are added. Thematerials are heated further to remove one and one-half parts of anaqueous distillate with a maximum final temperature of 260 C. Thematerial is cooled, and 375 parts of a suitable hydrocarbon extract isadded to give the finished product.

Example IX In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 1200 parts by weight ofa polyglycol prepared by adding 6 moles of ethylene oxide terminally toa mole of polypropylene glycol 2700, grams diglycolic acid and grams ofa suitable hydrocarbon extract. The materials are heated to remove 17parts of an aqueous distillate with a maximum final temperature of 265C.

Then, 366 parts of the above intermediate and 110 parts of theoxyalkylated resin of Example L are heated to remove 1.2 parts ofaqueous distillate with a maximum final temperature of 270 C. Fourhundred parts of a suitable hydrocarbon extract is added to give thefinished product.

Example X In a manner similar to Example IX, 244 parts of theintermediate of Example IX and 200 parts of theoxyalkylated resin ofExample L were heated together to remove one and one-half parts ofaqueous distillate with a maximum final temperature of 260 C. Aftercooling, 375 partsof a suitable hydrocarbon extract was added to givethe finished product.

Example XiI In a. manner similar to Example 1X, 122 parts of theintermediate of Example IX and 300 parts of the oxyalkylated resin ofExample L were heated to remove one part of aqueous distillate with amaximum final temperature of 265 C. After cooling, 375 parts of asuitable hydrocarbon extract was added to give the finished product.

Example XII In a three-necked reaction flask provided with means ofmechanical stirring and heating, there is added 300 parts of apolypropylene glycol of 3000 molecular weight. Forty grams of diglycolicacid and 50 grams of a suitable hydrocarbon extract are added, and thematerial heated to remove 7 parts of aqueous distillate with a maximumfinal temperature of 270 C. The material was then cooled to 150 C., and200 parts of the oxyalkylated resin of Example M was added. The materialwas then heated to remove 2 parts of aqueous distillate at a maximumfinal temperature of 270 C. After cooling, 375 parts of a suitablehydrocarbon extract was added to give the finished product.

Example XIII In a manner similar to Example X11, 200 parts of theoxyalkylated resin of Example N was substituted for the 200 parts of theoxyalkylated resin of Example M.

Example XIV Example XV There is charged in a Dowtherm vessel 8000 lbs.of polypropylene glycol (mol. wgt. 2700) to which has been added byoxyethylation 6 mols of ethylene oxide, 1050 lbs. of diglycolic acid,and 180 gallons of S0 extract. The mixture is heated until 18 gallons ofaqueous distillate are recovered with a maximum final temperature ofabout 270 C. The batch is'held at 265270 C. for about one-half hour andis then cooled to 200 C. The cooled product is blended uniformly with220 gallons of S0 extract.

Then 1800 lbs. of this product is mixed with 5400 lbs. of the product ofExample R and 20 gallons of S0 extract. They .are heated to about C.over a period of about two hours and held at 190-200 C. for anotherhour. The temperature is then slowly raised to 260 C.

and 4 to 4.5 gallons of aqueous distillate is distilled off andcollected. The reactants are held at 255-260 C. for one-half hour. Theproduct is cooled to 200 C. and

blended with 900 gallons (6750 lbs.) of S0 extract. The product is thenfiltered at about 90 C.

1 1 Example X Vxl There is charged in a Dowtherm vessel 8000 lbs. ofpolypropylene glycol (mol. wgt. 2700) to which has been added byoxyethylation 6 mols of ethylene oxide, 1050 lbs. of diglycolic acid,and 180 gallons of S extract. The mixture is heated until 18 gallons ofaqueous distillate are recovered with a maximum final temperature ofabout 270 C. The batch is held at 265-270 C. for about one-half hour andis then cooled to 200 C. The cooled product is blended uniformly with220 gallons of S0 extract.

Then 1800 lbs. of this product is mixed with 5400 lbs. of the product ofExample S and 20 gallons of S0 extract. They are heated to about 190 C,over a period of about two hours and held at 190200 C. for another hour.The temperature is then slowly raised to 255 C. and 4 to 4.5 gallons ofaqueous distillate is distilled off and collected. The reactants areheld at 255260 C. for one-half hour. The product is cooled to 200 C. andblended with 910 gallons of S0 extract. The product is then filtered atabout 90 C.

Example XVII There is charged in a Dowtherm vessel 8000 lbs. ofpolypropylene glycol (mol. wgt. 2700) to which has been added byoxyethylation 6 mols of ethylene oxide, 1050 lbs. of diglycolic acid,and 180 gallons of S0 extract. The mixture is heated until 18 gallons ofaqueous distillate are recovered with a maximum final temperature ofabout 270 C. The batch is held at 265-270 C. for about one-half hour andis then cooled to 200 C. The cooled product is blended uniformly with220 gallons of S0 extract.

Then 1800 lbs. of this product is mixed with 5400 lbs. of the product ofExample T and 20 gallons of S0 extract. They are heated to about 190 C.over a period of about two hours and held at l90200 C. for another hour.The temperature is then slowly raised to 255 C.

and 3 to 3.5 gallons of aqueous distillate is distilled off andcollected. The reactants are held at 255-260" C. for one-half hour. Theproduct is cooled to 200 C. and blended with 910 gallons of S0 extract.The product is then filtered at about 90 C.

Among the suitable hydrocarbon vehicles which can be employed asdiluentsand reaction solvents is sulfur dioxide extract. This materialis a by-product from the Edeleanu process of refining petroleum in whichthe undesirable fractions are removed by extraction with liquid sulfurdioxide. After removal of the sulfur dioxide a mixture of hydrocarbon,substantially aromatic in character, remains and is designated in thetrade as sulfur dioxide extract or S0 extract. Examples of othersuitable hydrocarbon vehicles and solvents are toluene, xylene, gas oil,diesel fuel, bunker fuel and coal tar solvents. The above cited examplesof solvents are adaptable to azeotropic distillation as Would also beany other solvent which is immiscible with water, miscible with thereacting mass and has a boiling point or boiling range in excess of theboiling point of water.

DEMULSIFICATION mulsifying agent to 2,00050,000 parts of the emulsion,

and thereafter allowing the emulsion to remain in a relatively quiescentstate during which separation of the oil and water occurs. Thedemulsifying agents of this invention may be used in conjunction withother demulsifying agents from classes such as the petroleum sulfonatetype, of which naphthalene sulfonic acid is an example, the modifiedfatty acid type, the amine modified oxyalkyl- 'ated phenol-formaldehydetype, and others.

12 The effectiveness of the compositions of this invention asdemulsifying agents is illustrated in the following tests and data.

BOTTLE TESTING OF CRUDE OIL EMULSIONS The bottle testing of. crude oilemulsions is conducted according to the following procedure: freshsamples of the emulsion-breaking chemicals in organic solvents solutionare prepared in 10% solutions. These solutions are made by accuratelydiluting 10 milliliters of the emulsion-breaking chemicals inmilliliters of a mixture of equal parts of anhydrous isopropyl alcoholand an aromatic hydrocarbon such as xylene. The mixture is agitated welluntil the emulsion-breaking chemical is completely dissolved.

The equipment for running the crude oil emulsionbreaking test, inaddition to the foregoing 10% solutions, includes a set of six ouncesgraduated prescription bottles, a funnel, a graduated 0.2 milliliterpipette, a thief pipette, a centrifuge, centrifuge tubes and athermometer. The graduated prescription bottles are filled to themilliliter mark with the crude oil emulsion to be tested, preferably asample which has been recently collected. If there is any free water inthe crude oil emulsion sample collected, it is bled off before thebottles are filled. Each bottle is inverted several times with the thumbover the opening of each bottle so that the bottle will be coated withan emulsion film.

By means of the 0.3 milliliter pipette, the prescribed volume of the 10%solution of the emulsion-breaking chemical is added to the emulsion inthe bottles. The bottles are then capped and given manual agitation fora predetermined number of counts. The number of counts are determined bya survey of the agitation which can be secured in the system in whichthe crude oil emulsion is being used. If the emulsion requires heat fortreatment, the bottles are placed in hot Water bath, the length of timeand temperature determined by the particular plant equipment andpractice in which the particular emulsion is employed. If the plantprovides for hot agitation of the emulsion the bottles may be given acorresponding amount of manual hot agitation.

The bottles are then removed from the hot Water bath and the water drop,presence of the bottom settlings (B.S.) layer and color and generalappearance of the oil are noted.

A thief grind-out is taken on all bottles which appear to be promising.A thief grind-out is made by preparing centrifuge tubes filled withgasoline to the 50% mark. The thief pipette is set to the properlengthby adjusting the rubber stopper so that the bottom of the pipette isabout A inch above the oil-water level of the bottle with maximum waterdrop. This same setting is used for all subsequent thiefings orremaining bottles. The thiefed oil from each bottle is added to thecentrifuge tube to the 100% mark, and the tube'is shaken. The samplesare then centrifuged for three minutes.

With certain parafiin base oils a portion of the parafiin is thrown downwith the 13.8. If the centrifuge tubes are heated to F. the paraffinwill melt and be dissolved in the gasoline-oil mixture and usually willnot be thrown down again with the B.S. upon centrifuging while hot.However, occasionally the parafiin will re-congeal as the tube coolsduring centrifuging. If this occurs, the tube is removed from thecentrifuge and heated to 150 F. without shaking or disturbing thesettled B.S. layer. The heated sample is then centrifuged for 15seconds.

This should give a true B.S. reading free of paraflin.

An excess chemical grind-out is then run on each centrifuge by addingseveral drops of a 20% solution in white gasoline or other solvent of achemical which causes complete separation of the water and oil. Withsome sensitive emulsions the chemical will cause reemulsification. Inthese instances it is necessary to rethief and add a lesser amount. Eachtube is vigorously shaken to make sure that .the packed B.S. layer isbroken up and the tubes heated to 150 F. in the case of troublesomeparaffin base crude oil. The samples are then centrifuged for threeminutes.

During the test the speed of the Water drop is observed carefully afterthe emulsion-breaking chemical is added of Examples I and III at a ratioof 0.02 part of a solution of the treating chemical to 100 parts of theemulsion fluid. The samples weregiven 150 cold shakes and 50 hot shakes,the hot temperature being 120 F. A summary of the observations madeduring the test ap pears in the following table.

to the prescription bottles. The observation of the color and brillianceof the oil in transmitted light is very important. In general, thebrilliance and depth of color increases with a decrease in B5. & W.(bottom settlings and water) content. The observations of color are madein the oil in the prescription bottles before and after heat treatment.In the ideal treatment of crude oil emulsions the oil-water line couldbe a sharp, clean line without any web or sludge present. Presence of aconsiderable amount of sludge or web is undesirable because this foreignmaterial will eventually go to stock in the treating plant and bereported as B. S. Trades of web or sludge, however, will disappear or beremoved in the normal treating plant.

In almost all instances the thief grind-out and excess chemicalgrind-out readings indicate the formula that has most nearlyproducedcrude oil free from BS. and water. The most efiicientemulsion-breaking chemical is determined by the foregoing test procedureby the overall consideration of the following, factors: relative speedof the breaking of the emulsion which is usually indicated by speed ofwater drop, color and brilliance of the oil layer, the relative absenceof web or sludge at oil-water line and the ability to most nearlyproduce treated oil that is free from 3.8. and water.

By way of illustrating the effectiveness of the emulsion- .breakingchemicals contemplated by this invention the composition of Example Iwas tested according to the foregoing bottle testing procedure onsamples of 24 gravity crude oil obtained from Esperson Dome Field,Texas. The crude oil emulsion contained about 56% water. The commercialtreating chemical being used on the lease and the treating chemical ofExample I were both tested for comparative purposes. These treatingchemicals were added at a ratio of 0.06 part of a 10% solution, asdescribed in the foregoing procedure, to 100 parts of the emulsionfluid. The samples were given 150 shakes cold and 50 shakes hot, the hottemperature being 120 F. The observations made during the tests wererecorded and are summarized in the following table.

Similar tests were made on a crude oil emulsion containing about 42%water of a 24 gravity crude oil from a lease in Esperson Dome Field. Thetreating chemicals tested included the commercial demulsitying agentbeing used on the lease in addition to the treating compositions Othersimilar tests were made on a crude oil emulsion containing about 56%water of a 28 gravity crude oil from Spivey Field, Kansas. The treatingchemicals tested were the commercial demulsifying agent being used onthe lease in addition to the treating composition of Example I at aratio of 0.06 part of a 10% solution of the testing chemical to parts ofthe emulsion fluid. The samples were given cold shakes and 50 hotshakes, the hot temperature being F. A summary of the observations madeduring the test appears in the following table.

TABLE III Water Drop Thief Grind- Excess Grind- Out Out TreatingChemical 15 min. 60 (t% l)70 min. B.S. Water B.S. Water CommercialChemical 14 42 5.8 0.2 0 5.6 Example III 41 50 0 0.8 0 1.5

The invention is hereby claimed as follows: a 1. A process for breakingemulsions of the water-in-oil type which comprises subjecting theemulsion to the action of a dicarboxylic acid mixed ester in which theester com- :ponents consist of (a) an oxyalkylatedorganic-solventsoluble phenol-formaldehyde condensation product having4-15 phenolic nuclei, said phenol being a monoalkyl phenol with a 5-15carbon alkyl group, the weight ratio of alkylene oxide to condensationproduct falling between about 1:2 and 9:1, respectively, thephenol-formaldehyde condensation product being oxyalky-lated withethylene oxide and propylene oxide, the ratio of propylene oxide toethylene oxide being at least 1:4, respectively, and (b)polyoxyalkyl-ene glycol having a molecular weight of at 'least 1200,said glycol selected from the group consisting of polyoxypropyleneglycol and oxyethylene, oxypropylene glycol in a weight ratio ofoxyethylene to oxypropylene not exceeding 4:1, the weight ratio ofoxyalkylated condensation product to polyoxya-lkylene glycol beingbetween 1:4 and 4: 1, and (c) an organic, dicarboxy acid, the esterifiedcarboxyl groups of the dicarboxy acid nuclei of said ester beingesterified with both components (a) and (b), the mol ratio in said esterof said dicarboxy acid to the total mols of (a) and (b) being in therange of 1-221, respectively, and said ester further having awater-solubility of not more than two parts by weight per 100 parts ofdistilled water at equilibrium at 70 F.

2. A process for breaking emulsions of the water-in-oil type whichcomprises subjecting the emulsion to the action of .a dicarboxylic acidmixed ester in which the ester components consist of (a) an oxyalkylatedorganic-solventsoluble monoalkyl phenol-formaldehyde condensationproduct having 4-15 phenolic nuclei, the alkyl group of said phenolhaving between 4 and 15 carbons inclusive, the weight ratio of alkyleneoxide to condensation product falling between about 1:2 and 15:1respectively, the phenol-formaldehyde condensation product beingoxyalkylated with ethylene oxide and propylene oxide, the ratio ofpropylene oxide to ethylene oxide being 1:4 to 25:1, respectively, and(b) polyoxyalkylene glycol having a molecular weight of at least 1200,said glycol selected from the group consisting of polyoxypropyleneglycol and oxyethylene, oxypropylene glycol in a weight ratio ofoxyethylene to oxypropylene not exceeding 4: 1, the weight ratio ofoxyalklated condensation product to polyoxyalkylene glycol being between1:5 and 5:1, and (c) an organic, dicarboxy acid, the esterified carboxylgroups of the dicarboxy acid nuclei of said ester being esterified withboth components (a) and (b), the mol ratio in said ester of saiddicarboxy acid to the total mols of (a) and (b) being in the range of1-2: 1, respectively, and said ester further having a water-solubilityof not more than two parts by weight per 100 parts of distilled water atequilibrium at 70 F.

3. A process for breaking emulsions of the water-in-oil type whichcomprises subjecting the emulsion to the action of a water insoluble,dicarboxylic acid mixed ester in which the ester components consist ofa) an oxyalkylated organic-solvent-soluble alkyl phenol-formaldehydecondensation product having 4-15 phenolic nuclei, said alkyl phenolbeing primarily a monoalkyl phenol containing not greater than about 25%dialkyl phenol, the alkyl group having between 4 and carbons inclusive,the weight ratio of alkylene oxide to condensation product fallingbetween about 1:2 and 15 1, respectively, the phenol-formaldehydecondensation product being oxyalkylated with ethylene oxide andpropylene oxide, the ratio of propylene oxide to ethylene oxide being1:4 to :1, respectively,

and (b) a polyoxyalkylene glycol having a molecular Weight of at least1200, said glycol selected from the group consisting of polyoxypropyleneglycol and oxyethylene, oxypropylene glycol in a weight ratio ofethylene oxide to propylene oxide not exceeding 421, the weight-ratio ofoxyalkylated condensation product to polyoxyalkylene glycol beingbetween about 1:5 and 5: 1, and (c) an organic, dicarboxy acid, theesterified carboxyl groups of the dicarboxy acid nuclei of said esterbeing esterified with both components (a) and (b), the mol ratio in saidester of said dicarboxy acid to the total mols of (a) and (b) being inthe range of 1-2: 1, respectively, and said ester further having awater-solubility of not more than two parts by weight per 100 parts ofdistilled water at equilibrium at 70 F.

4. A process for breaking emulsions of the water-in-oil type whichcomprises subjecting the emulsion to the action of a water insoluble,dicarboxylic acid mixed ester in which the ester components consist of(a) an oxyalkylated organic-solvent-soluble alkyl phenol-formaldehydecondensation product having 4-15 phenolic nuclei, said phenol beingprimarily a monoalkyl phenol, the alkyl group having between 4 and 15carbons inclusive, the weight ratio of alkylene oxide to, condensationproduct falling between about 1:2 and 15: 1, respectively, thephenol-formaldehyde condensation product being oxy-alkylated withethylene oxide and propylene oxide, the ratio of propylene oxide toethylene oxide being 1:4 to 25: 1, respectively, and (b)poly-oxypropylene glycol having a molecular weight of at least 1200, theWeight ratio of oxyalkylated condensation product to polyoxypropyleneglycol being between about 1:5 and 5: 1, and (c) an organic, dicarboxyacid, the esterified carboxyl groups of the dicarboxy acid nuclei ofsaid ester being esterified with both components (a) and ('b), the molratio in said ester of said dicarboxy acid to the total mols of (a) and(b) being in the range of 12:1, respectively, and said ester furtherhaving a water-solubility of not more than two parts by weight per 100parts of distilled water at equilibrium at F.

5. A process for breaking emulsions of the water-in-oil type whichcomprises subjecting the emulsion to the action of a water insoluble,dicarboxylic acid mixed ester in which the ester components consist of(a) an oxyalkylated organic-solvent-soluble alkyl phenol-formaldehydecondensation product having 4-15 phenolic nuclei, said alkyl phenolbeing primarily a monoalkyl phenol, the alkyl group having between 4 and15 carbons inclusive, the Weight ratio of alkylene oxide to condensationproduct falling between about 1:2 and 15: 1, respectively, thephenol-formaldehyde condensation product being oxyalkylated withethylene oxide and propylene oxide, the ratio of propylene oxide toethylene oxide being 1:4 to 25:1, respectively, and (b) apolyoxyalkylene glycol comprising oxyethylene, oxypropylene glycol in aratio of oxyethylene to oxypropylene not exceeding 4:1, the Weight ratioof oxyalkylated condensation product to polyoxyalkylene glycol beingbetween about 1:5 and 5:1, and (c) an organic, dicarboxy acid, theesterified carboxyl groups of the dicarboxy acid nuclei of said esterbeing esterified with both components (a) and (b), the mol ratio in saidester of said dicarboxy acid to the total mols of (a) and (b) being inthe range of 1-2: 1, respectively, and said ester further having awater-solubility of not more than two parts by Weight per parts ofdistilled Water at equilibrium at 70 F.

6. The process of claim 2 wherein said dicarboxy acid is diglycolicacid.

7. The process of claim 2 wherein said dicarboxy acid is maleic acid.

8. The process of claim 2 wherein said dicarboxy acid is pht-halic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,454,544 11/48Bock et a1 26053 2,454,545 11/48 Bock et al 260-342 2,541,999 2/51 DeGroote et al. 252342 2,766,213 10/56 Dickson 252-342 2,841,563 7/58Kirkpatrick et al 252342 JULIUS GREENWALD, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,202,615 August 24, 1965 Willard H. Kirkpatrick et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

In the grant, lines 2 and 3, and line 13, and in the heading to theprinted specification, line 5, name of assignee, for "Valco ChemicalCompany", each occurrence, read" Na lco Chemical Company Signed andsealed this 20th day of September 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER 'ioner-ofPatems Attestisg Officer

1. A PROCESS FOR BREAKING EMULSIONS OF THE WATER-IN-OIL TYPE WHICHCOMPRISES SUBJECTING THE EMULSION TO THE ACTION OF A DICARBOXYLIC ACIDMIXED ESTER IN WHICH THE ESTER COMPONENTS CONSIST OF (A) AN OXYALKYLATEDORGANIC-SOLVENTSOLUBLE PHENOL-FORMALDEHYDE CONDENSATION PRODUCT HAVING4-15 PHENOLIC NUCLEI, SAID PHENOL BEING A MONALKYL PHENOL WITH A 5-15CARBON ALKYL GROUP, THE WEIGHT RATIO OF ALKYLENE OXIDE TOCONDENSATIONPRODUCT FALLING BETWEEN ABOUT 1:2 AND 9:1, RESPECTIVELY, THEPHENOL-FORMALDEHYDE CONDENSATION PRODUCT BEING OXYALKYLAATED WITHETHYLENE OXIDE BEING AT LEAST 1:4, RESPECTIVELY, AND (B) POLYOXYALKYLENEGLYCOL HAVING A MOLECULAR WEIGHT OF AT LEAST 1200, SAID GLYCOL SELECTEDFROM THE GROUP CONSISTING OF POLYOXYPROPPYLENE GLYCOL AND OXYETHYLENE,OXYPROPYLENE GLYCOL IN A WEIGHT RATIO OF OXYETHYLENE TO OXYPROPYLENE NOTEXCEEDING 4:1, THE WEIGHT RATIO OF OXYALKYLATED CONDENSATION PRODUCT TOPOLYOXYALKYLENE GLYCOL BEING BETWEEN 1:4 AND 4:1, AND (C) AN ORGANIC,DICARBOXY ACID, THE ESTERIFIED CARBOXYL GROUPS OF THE DICARBOXY ACIDNUCLEI OF SAID ESTER BEING ESTERIFIED WITH BOTH COMPONENTS (A) AND (B),THE MOL RATIO IN SAID ESTER OF SAID DICARBOXY ACID TO THE TOTAL MOLS OF(A) AND (B) BEING IN THE RANGE OF 1-2:1, RESPECTIVELY, AND SAID ESTERFURTHER HAVING A WATER-SOLUBILITY OF NOT MORE THAN TWO PARTS BY WEIGHTPER 100 PARTS OF DISTILLED WATER AT EQUILIBRIUM AT 70*F.